US8791173B2 - Ink composition for forming insulating film and insulating film formed from the ink composition - Google Patents

Ink composition for forming insulating film and insulating film formed from the ink composition Download PDF

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US8791173B2
US8791173B2 US12/737,145 US73714509A US8791173B2 US 8791173 B2 US8791173 B2 US 8791173B2 US 73714509 A US73714509 A US 73714509A US 8791173 B2 US8791173 B2 US 8791173B2
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ink composition
insulating film
organic solvent
mass
ink
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US20110086946A1 (en
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Masayoshi Kotake
Hideki Etori
Toshihiro Ebine
Hiroshi Isozumi
Masanori Kasai
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DIC Corp
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DIC Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H01L21/02288—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating printing, e.g. ink-jet printing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to an ink composition for forming an insulating film, which can be used for production of an electronic device, and an insulating film formed from the ink composition.
  • Transistors are extensively used as an important electronic device (electronic component) which constitutes televisions or computer equipment, and today, they are produced using inorganic substances such as silicon as a main material. Recently, an organic transistor (OFET) using organic substances as the transistor member (refer to Non Patent Document 1) has attracted attention.
  • OFET is soft and flexible, and has an advantageous benefit in that raw materials of OFET can be produced at low cost per unit area since raw materials of OFET is inexpensive; therefore, OFET is considered to be an indispensible item for the make up of ubiquitous computing age, that is, an essential component for realizing flexible and low-cost terminals.
  • OFET is an electronic device which includes three electrodes, an insulating layer, and a semiconductor layer as essential members.
  • An example of the device structure is shown in FIG. 1 .
  • a method for forming a gate insulating layer (GI) which corresponds to a reference number 3 in the FIGURE, includes a wet process such as a printing method and a dry process such as vacuum deposition or sputtering, the wet process is preferable to lower the cost (refer to Non Patent Document 2). Meanwhile, usually, it is necessary for the wet process to go through a superheating (sintering) process after the film is produced. When flexible materials having a low heat resistance temperature are used for substrates, it is required for the superheating (calcination) process to be conducted at a lower temperature.
  • the calcination temperature needs to be 150° C. or lower.
  • ink which is used for forming an insulating film it is required for ink which is used for forming an insulating film to have an excellent printing property in order to facilitate the formation of a fine pattern.
  • the GI there are properties which concern a device production process, and properties which concern the electric property (FET property) of a device.
  • FET property electric property
  • the former there is a property of insolubility to a solvent (that is, solvent resistance) which is used for an organic semiconductor layer placed on the GI.
  • solvent resistance that is, solvent resistance
  • a polyvinylphenol-based material (I) using polyimide-based materials as a curing agent is known (refer to Non Patent Document 3); also, polyvinylphenol-based materials using melamine-based resins as a curing agent are known (refer to Non Patent Document 4).
  • thermoplastic resin represented by polyraethylmethacrylates and polystyrenes is also known (refer to Non Patent Document 5).
  • the thermoplastic resin has poor solvent resistance, and it is difficult to laminate a conductive layer, a semiconductor layer, and the like on the thermoplastic layer by the printing method; therefore, the dry process which needs facilities for deposition or the like is required.
  • Patent Document 6 a solid or liquid type bisphenol general-purpose epoxy resin (III) is also known (refer to Non Patent Document 6).
  • Patent Document 1 insulating materials including a silane coupling agent and an epoxy resin are disclosed (refer to Patent Document 1).
  • Patent Document 2 a method for producing a circuit device by a letterpress plate reverse printing method is disclosed, there is no disclosure regarding low-temperature calcination (refer to Patent Document 2). Accordingly, there is no ink technique for forming an insulating film which is sufficiently equipped with an insulating property, solvent resistance, and a calcination temperature to form an electronic device by providing the insulating film on a flexible substrate. Also, in the current circumstances, there is no ink technique for forming the insulating film which has sufficient ability for forming a fine pattern.
  • a first purpose of the present invention is to provide an insulating ink composition for forming an insulating film, which sufficiently achieves a target calcination temperature, solvent resistance, and an insulating property.
  • a second purpose of the invention is to provide an ink composition for forming an insulating film which can form, by the printing method, fine insulating film patterns necessary for formation of highly integrated organic transistors.
  • a third purpose of the invention is to provide an insulating film which is formed from the ink composition.
  • the invention provides an ink composition, which forms an insulating film, wherein the ink composition includes, as essential components, an organic solvent, a polyvinylphenol-based resin, an epoxy resin, and a cross-linking aid.
  • the invention provides an ink composition, which forms an insulating film, wherein the ink composition can form fine insulating film patterns, and the organic solvent includes an organic solvent which has a vapor pressure of 11.3 ⁇ 10 2 Pa or higher at 20° C. and a boiling point of lower than 115° C. under atmospheric pressure and an organic solvent which has a vapor pressure of less than 11.3 ⁇ 10 2 Pa at 20° C. and a boiling point of 115° C.
  • the ink composition includes a extender component having a volume average particle diameter of 1 nm to 150 nm and a silicone-based releasing component, the ink surface tension is 17 mN/m to 30 mN/m at 25° C., and the ink viscosity is 0.5 mPa ⁇ s to 30 mPa ⁇ s.
  • the invention provides an insulating film formed from the ink composition for forming an insulating film.
  • the ink composition for forming an insulating film of the invention it is possible to obtain an excellent property of the insulating film at a calcination temperature of 100° C. to 140° C., and to form the insulating film on a flexible substrate such as a PEN.
  • the insulating film formed has solvent resistance, and it is possible to laminate a conductive layer, semiconductor layer and other layers on the insulating film by the printing method.
  • leakage current is small, it is possible to properly use the insulating film as a gate insulating film for an organic field-effect transistor (OFET) or the like.
  • OFET organic field-effect transistor
  • FIG. 1 is a schematic configuration view which shows an example of an electronic device wherein the insulating film, of the invention is used.
  • the ink composition for forming an insulating film of the invention includes, as essential components, an organic solvent, a polyvinylphenol-based resin, an epoxy resin, and a cross-linking aid.
  • organic solvents used for the ink composition for forming an insulating film of the invention any solvent which dissolves the polyvinylphenol-based resin can be used.
  • examples thereof include aliphatic hydrocarbon-based organic solvents such as pentane, hexane, heptane, octane, decane, dodecane, isopentane, isohexane, isooctane, cyclohexane, methylcyclohexane, and cyclopentane; aromatic hydrocarbon-based solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, mesithylene, naphthalene, cyclohexylbenzene, and diethylenebenzene; ester-based solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethy
  • Examples of the polyvinylphenol-based resin used for the ink composition for forming an insulating film of the invention includes p-vinylphenol homopolymer; copolymer of p-vinylphenol with other vinyl monomers (for example, methyl methacrylate, 2-hydroxylethyl methacrylate, styrene, butyl acrylate, 2-hydroxylethyl acrylate, phenylmaleimide, maleic acid, and fumaric acid); homopolymer of bromine-substituted p-vinylphenol obtained by substituting p-vinylphenol with bromine; copolymer of bromine-substituted p-vinylphenol with other vinyl resins; homopolymer of p-vinylphenol derivatives obtained by sulfonating, t-butylating, or aminating p-vinylphenol; copolymer of p-vinylphenol derivatives with other vinyl monomers.
  • vinyl monomers for example,
  • polyvinylphenol-based resin is not particularly limited to the resins. These resins can be used alone or in combination of two or more kinds thereof.
  • the content of the polyvinylphenol-based resin is preferably 10% by mass or more, and more preferably 25% by mass or more, based on the total solid content of the ink composition for forming an insulating film excluding extender pigment.
  • Epoxy resin which is used for the ink composition for forming an insulating film of the invention, functions as a cross-linking agent for polyvinylphenol-based resin, and any known and widely used epoxy resin having two or more reactable functional epoxy groups may be used.
  • examples thereof include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, polyfunctional epoxy resin, flexible epoxy resin, brominated epoxy resin, glycidyl ester-type epoxy resin, polymer-type epoxy resin, or biphenyl-type epoxy resin.
  • epoxy resin is not particularly limited to these resins. These resins can be used alone or in combination of two or more kinds thereof.
  • the ink composition for forming an insulating film of the invention uses a cross-linking aid.
  • the cross-linking aid include widely known and used cross-linking aids may be used, in addition to amine compounds, polyamide resins, imidazoles, polymercaptans, bromine trifluorides, dicyandiamides, organic acid hydrides, and triphenylphosphine. These cross-linking aids can be used alone or in combination of two or more kinds thereof. From the viewpoint of stability at a room temperature and curing at a low temperature of 150° C. or lower, 2-ethyl-4-methyl imidazole is preferable.
  • the content of the cross-linking aid is 0.3% to 10.0% by mass, and preferably 1.0% to 5.0% by mass, based on the total solid content. If the content thereof is out of the above range and is too small, curing is insufficient. If the content thereof is too large, the cross-linking aid having strong polarity remains in the obtained insulating resin film, thereby leading to a problem of inhibiting insulating property, and thus is not preferable.
  • the content of the cross-linking aid is 0.3% to 10.0% by mass, and preferably 1.0% to 5.0% by mass, based on the total solid content excluding the extender component.
  • the ink composition for forming an insulating film of the invention can be used by adding, if necessary, releasing agents, extender components, various surfactants which are mainly used for adjusting ink surface tension or improving a leveling property, or the like.
  • hydrocarbon-based surfactants silicone-based surfactants, fluorine-based surfactants, and mixtures of two or more kinds thereof can be used.
  • fluorine-based surfactant is excellent in adjusting ink surface tension and effective in improving leveling property.
  • the insulating film formed from the ink having the fluorine-based surfactant added thereto is excellent in terms of compatibility with crystalline organic semiconductors such as polythiophene. Therefore, the fluorine-based surfactant is the most preferable surfactant, since the surfactant can be expected to improve transistor characteristics as well as ink properties.
  • the surfactant which has a linear perfluoroalkyl group and chain length of C6 or more is preferable, and the nonionic fluorine-haled surfactant with C8 or more is more preferable.
  • Specific examples thereof include MEGAFAC F-482, MEGAFAC F470 (R-08), MEGAFAC F472SF, MEGAFAC R-30, MEGAFAC F-484, MEGAFAC F-486, MEGAFAC F172D, MEGAFACE F178RM (all trade names, manufactured by DIC Corporation).
  • the surfactant is not particularly limited thereto. Also these surfactants can be used alone or in combination of two or more kinds thereof.
  • the content of the surfactants are, as active ingredients, 0.01% to 5.0% by mass, and preferably 0.05% to 1.0% by mass, based on the total ink composition.
  • substrates for forming electronic devices include glass fiber reinforced plastic such as a glass woven fabric epoxy plate, a glass non-woven fabric epoxy-laminated plate, a paper epoxy-laminated plate, a paper phenol-laminated plate, and a glass woven fabric polyimide-laminated plate; plastic films such as polyethylene naphthalate, polyimide, polyethylene terephthalate, and polycarbonate; metal foils and metal plates such as copper coated with insulant, aluminum, stainless steel, or iron; or plate-like glass, alumina, zirconia, and silica. It is possible to promote a curing property at low temperature, which is a characteristic of the invention, by using flexible plastic materials such as polyethylene naphthalate, polyethylene terephthalate, and polycarbonate, in particular.
  • the ink composition for forming an insulating film of the invention into a film various printing methods can be employed. Widely known and used printing methods and methods for producing coated substances with a single layer or multiple layer structure can be employed. Specifically, examples of such methods include a gravure method, an offset method, a letterpress plate method, a screening method, a reversing method, an air doctor coating method, a blade coating method, an air knife coating method, a squeeze coating method, an immersion coating method, a transfer roller coating method, a kiss coating method, a cast coating method, a spray coating method, a die method, a spin coating method, a bar coating method, a micro contact method, and a letterpress plate reverse printing method.
  • the ink composition of the invention includes proper additives, selects proper solvents, and is produced with the proper resin component concentration, depending on each of the printing methods.
  • the letterpress plate reverse printing method which can pattern, for example, fine lines with good reproduction are more preferably used.
  • the letterpress plate reverse printing method herein is a method which includes coating ink on a smooth surface which has a releasing property and consists of polydimethylsiloxane (PDMS) or the like, pressing a letterpress plate serving as a stamp plate on the ink-coated surface, removing an ink portion contacting the letterpress plate from the surface having the releasing property, and reversely transferring the remaining pattern to a substance to be printed.
  • PDMS polydimethylsiloxane
  • the ink composition for forming an insulating film of the invention which is suitable for this printing method, preferably includes two or more kinds of quick drying or slow drying solvents, extender components, surface energy adjusting agents, and releasing agents, in addition to the essential components. By adding these components, it is possible to improve an ink printing property, and to realize a fine pattering property which is necessary for constructing an electronic device such as an organic transistor.
  • the quick drying organic solvent one or more solvents which have vapor pressure of 11.3 ⁇ 10 2 Pa (8.5 mmHg) or higher at 20° C. and a boiling point of lower than 115° C. under atmospheric pressure can be used.
  • the content of the quick drying organic solvent is 5.0% to 90.0% by mass, preferably 10.0% to 60.0% by mass, and more preferably 20.0% to 40.0% by mass, based on the total ink composition.
  • the quick drying organic solvent is selected depending on the solubility of the resin, and the affinity for the pigment dispersing system.
  • ester-based solvents such as ethyl acetate, normal propyl acetate and isopropyl acetate
  • alcohol-based solvents such as methanol, ethanol, 1-propanol, and 2-propanol
  • hydrocarbon-based solvents such as pentane, hexane, cyclohexane, methylcyclohexane, toluene, and xylene
  • ketone-based solvents such as tetrahydrofuran.
  • the solvent can be used as a mixture of solvents from the single category or a mixture of solvents from the plural category.
  • isopropyl acetate, ethanol, and 2-propanol are preferable in terms of the evaporation rate and surface tension thereof.
  • any one or more solvents which have vapor pressure of less than 11.3 ⁇ 10 2 Pa (8.5 mmHg) at 20° C. and a boiling point of 115° C. or higher under atmospheric pressure can be used.
  • the content of the slow drying organic solvent is 5.0% to 90.0% by mass, preferably 30.0% to 70.0% by mass, and more preferably 40.0% to 60.0% by mass, based on the total ink composition.
  • These solvents are selected depending on the solubility of the resin, and the affinity for the pigment dispersing system.
  • ester-based solvents such as propylene glycol monomethyl ether acetate (PGMAc), 3-methoxy-3-methyl-butyl acetate, and ethoxyethyl propionate (EEP); alcohol-based solvents such as 1-butanol, DIADOL135 (trade name, manufactured by Mitsubishi Rayon Co., Ltd), 3-methoxy-3-methyl-1-butanol, 1-hexanol, 1,3-butanediol, 1-pentanol, 2-methyl-1-bunanol, and 4-methyl-2-pentanol; ether-based solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, and diethylene glycol e
  • solvents can be used as a mixture of solvents from the single category, or a mixture of solvents from the plural category.
  • solvents propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, and DIADOL 135 are preferable in terms of the evaporation rate and the surface tension thereof.
  • the releasing agent one or two or more kinds of known and widely used silicone-based compounds can be used. Specific examples thereof include dimethyl silicone oil, dimethyl silicone rubber, silicone resin, organic modified silicone, methylphenyl silicone oil, long-chain alkyl modified silicone oil, a mixture of a fluorine compound and a silicone polymer, and a fluorine modified silicone.
  • the releasing agent is not particularly limited thereto. Also these agents can be used alone or in combination of two or more kinds thereof.
  • KF-96L series (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable in terms of the releasing property and compatibility with PVP resin.
  • the content of the releasing agents is 0.0% to 5.0% by mass, preferably 0.0% to 1.0% by mass, based on the entire ink composition. If the content is out of the above range and too large, not only does the printing property decrease, but the problem of inhibiting insulating the film property occurs, and thus is not preferable.
  • one or two or more kinds of widely known and used a single color pigment, a single fine-particle powder, and a pigment dispersion obtained by dispersing the single color pigment or a single fine-particle powder in a dispersant or an organic solvent in advance can be used, as long as the components can maintain the insulating property of the coated film
  • Specific examples thereof include EXCEDIC BLUE0565, EXCEDIC RED0759, EXCEDIC YELLOW0599, EXCEDIC GREEN0358, and EXCEDIC YELLOWO648 (all trade names, manufactured by DIC Corporation); AEROSIL series (trade name, manufactured by Evonik Industries); SILYSIA, SYLOPHOBIC, SYLOPUTE, SYLOPAGE, SYLOPURE, SYLOSPHERE, SYLOMASK, SILWELL, and FUJI BALLOON (all trade names, manufactured by FUJI SILYSIA CHEMICAL LTD.); PMA-ST, and
  • extender component is not particularly limited to these materials. These components can be used alone or in combination of two or more kinds thereof. In order to improve the insulating property of the insulating film, it is preferable that these extender components inherently have a high electrical insulating property, and are homogenously and densely dispersed in the insulating film.
  • a high level of surface smoothness of the film is required. Consequently, average particle diameter of the extender components to be added to ink is preferably 1 nm to 150 nm, and more preferably 5 nm to 50 nm.
  • the average particle diameter of the extender components can be easily measured by, for example, a dynamic light scattering method.
  • the content of the extender components is 20% to 90% by mass, and preferably 40% to 70% by mass, based on the total solid content. If the content is out of the above range and is too large, the insulating film becomes brittle, and thus is not preferable. On the other hand, if the content is too small, the fine patterning property of ink becomes insufficient, and thus is not preferable.
  • ink appropriate to the letterpress plate reverse printing method includes the above-described composition
  • a physical property of the ink is also an important factor.
  • the ink viscosity at a temperature of 25° C. is within in a range of 0.5 mPa ⁇ s to 30.0 mPa ⁇ s. Within the range, a viscosity of 1.0 mPa ⁇ s to 5.0 mPa ⁇ s is more preferable.
  • the surface energy of the ink composition is also an important factor.
  • the surface energy of the ink composition is preferably 17 to 30 mN/m, but generally, a surface energy of less than 22 mN/m is preferable.
  • Ink of Example 1 was prepared by mixing 2.3 g of MARUKA LYNCUR-M (manufactured by Maruzen Petrochemical Co, Ltd) as a polyvinylphenol-based resin, 3.3 g of an epoxy resin EPICLON 850CPR (manufactured by DIC Corporation) as a cross-linking agent, 0.14 g of 2-ethyl-4-methylimidazole as a cross-linking aid, and 22.0 g of isopropyl acetate (hereinafter referred to as IPAc) as a solvent.
  • MARUKA LYNCUR-M manufactured by Maruzen Petrochemical Co, Ltd
  • EPICLON 850CPR manufactured by DIC Corporation
  • 2-ethyl-4-methylimidazole as a cross-linking aid
  • 22.0 g of isopropyl acetate (hereinafter referred to as IPAc) as a solvent 22.0 g of isopropyl acetate (hereinafter referred
  • Ink of Example 2 was prepared by mixing 2.3 g of poly(4-vinylphenol-co-methylmethacrylate) (manufactured by Sigma-Aldrich Co.) as a polyvinylphenol-based resin, 3.3 g of an epoxy resin EPICLON 850CPR (manufactured by DIC Corporation) as a cross-linking agent, 0.06 g of 2-ethyl-4-methylimidazole as a cross-linking aid, 22.0 g of cyclohexanone as a solvent, and 0.5 g of F-482 as a fluorine-based surfactant.
  • poly(4-vinylphenol-co-methylmethacrylate) manufactured by Sigma-Aldrich Co.
  • EPICLON 850CPR manufactured by DIC Corporation
  • 2-ethyl-4-methylimidazole as a cross-linking aid
  • 22.0 g of cyclohexanone as a solvent
  • F-482 0.5 g of F
  • Ink of Example 3 was prepared by mixing 2.3 g of MARUKA LYNCUR-M (manufactured by MARUZEN PETROCHEMICAL CO, LTD) as a polyvinylphenol-based resin, 3.3 g of an epoxy resin EPICLON 850CPR (manufactured by DIC Corporation) as a cross-linking agent, 0.15 g of a 2-ethyl-4-methylimidazole as a cross-linking aid, 15 g of IPAc as a solvent, 29 g of a propylene glycol monomethyl ether, 6.0 g of propylene carbonate, 2.0 g of KF96L-1cs (manufactured by Shin-Etsu Chemical Co., Ltd.) as a releasing agent, 1.0 g of F-482 (manufactured by DIC Corporation) and 0.3 g of MCF-350SF (manufactured by DIC Corporation) as fluorine-based surfactants; and 25 g of PM
  • Ink of Comparative Example 1 was prepared by mixing a polyvinylphenol-based resin as a resin component, 20.0 g of polymethyl methacrylate (PMMA) (manufactured by Sigma-Aldrich Co.: Mw 120,000) which was an acrylic resin used instead of an epoxy resin, 80.0 g of solvent cyclohexanone.
  • PMMA polymethyl methacrylate
  • Ink of Comparative Example 2 was prepared by mixing a polyvinylpehnol-based rein as a resin component, 20.0 g of a polystyrene resin (manufactured by Sigma-Aldrich Co.: Mw 44,000) which was used instead of an epoxy resin, 80.0 g of a solvent cyclohexanone.
  • Ink of Comparative Example 3 was prepared by mixing 20.0 g of MARUKA LYNCUR-M (manufactured by Maruzen Petrochemical Co, Ltd) as polyvinylphenol-based resin, 8.0 g of CYMEL-303 (manufactured by Nihon Cytec Industries Inc.) which was a cross-linking agent used instead of an epoxy resin, 100.0 g of a solvent cyclohexanone.
  • MARUKA LYNCUR-M manufactured by Maruzen Petrochemical Co, Ltd
  • CYMEL-303 manufactured by Nihon Cytec Industries Inc.
  • Ink of Comparative Example 4 was prepared by mixing 1.9 g of a phenol novolac resin (PHENOLITE TC-2090-60M: a solid content of 60% MEK solution), 2.0 g of an epoxy resin EPICLON 850CPR (manufactured by DIC Corporation), 0.1 g of 2-ethyl-4-methyl imidazole as a cross-linking aid, 4.0 g of isopropyl acetate (hereinafter referred to as IPAc) as a solvent, and 3.8 g of methyl ethyl ketone.
  • a phenol novolac resin PHENOLITE TC-2090-60M: a solid content of 60% MEK solution
  • EPICLON 850CPR manufactured by DIC Corporation
  • 2-ethyl-4-methyl imidazole as a cross-linking aid
  • IPAc isopropyl acetate
  • the inks obtained in the above Example 1 to Comparative Example 3 were made into films on the glass plates having thickness of 1.5 mm by a spin coater printing method so that the dried film thickness became 1 ⁇ m. Thereafter, the films were calcinated at 140° C. for 30 minutes to form samples for solvent resistance evaluation.
  • the solvent resistance evaluation was performed by immersing the respective glass plates on which the thin film formed as described above into butyl carbitol acetate for 20 hours and checking whether the thin film remained. The results are shown in Table 1 and Table 2.
  • the insulating film having a dried film thickness of about 1 ⁇ m was obtained by printing the respective ink composition on ITO-applied glass plates having thickness of 1.5 mm and calcinating at 140° C. for 30 minutes. Silver electrodes were formed on the insulating film by a vacuum deposition method, and current values at the time of applying 150V to the insulating film were measured. The unit is mAcm ⁇ 2 .
  • An image was formed by forming insulating ink-coated film on a PDMS surface of blanket by using the ink of Example 3, pressing the letterpress glass plate serving as a stamp plate on the coated film, removing extra ink to form a grid pattern having a line width of 20 ⁇ m on the blanket, and then transferring this pattern on a glass plate which was used as a substrate to be printed.
  • the quality of the image formed on the glass plate was observed with an optical microscope, and it was evaluated whether the pattern of the letterpress plate was accurately reproduced. The results are shown in Table 1.
  • a device for measuring a transistor property which has a bottom-gate bottom-contact (BGBC) structure shown in FIG. 1 , was prepared.
  • gate electrode A hard coat-applied PEN film having thickness of about 125 ⁇ m was cut into the predetermined size, conductive ink having silver nanoparticles evenly dispersed therein was evenly applied on the film by spin coating, and the resultant was calcinated in a clean oven at 150° C. for 40 minutes.
  • a gate insulating film having thickness of about 1 ⁇ m was formed by applying the ink for forming an insulating film of the invention by spin coating on the gate electrode formed from the conductive ink, and subjecting the resultant to thermal treatment in a clean oven at 140° C. for about 1 hour.
  • Source and drain electrodes Silver electrodes were formed by forming a source and drain electrode pattern having a channel length of 50 ⁇ m and width of 4 mm on the gate insulating film formed as above, by the letterpress plate reverse printing using conductive ink for reverse printing, and calcinating the resultant in a clean oven at 170° C. for 40 minutes.
  • P3HT thin film was formed on the insulating film, source and drain electrodes by spin coating and using 0.5% by weight of a xylene solution having an organic semiconductor Poly(3-hexylthiophene) (P3HT) therein.
  • the prepared device was subjected to thermal treatment in a glow box at 150° C. for about 5 minutes. Thereafter, Id-Vg and Id-Vd properties of the device were measured using a semiconductor parameter measuring apparatus (Keithley Instrument Inc., 4200). The degree of field-effect mobility and ON/OFF ratio were measured by a known method. The unit of degree of mobility is cm 2 /Vs.
  • Example 1 2 3 Solvent resistance ⁇ (Good) ⁇ (Good) ⁇ (Good) Leakage current ⁇ 10 ⁇ 5 ⁇ 10 ⁇ 5 ⁇ 10 ⁇ 5 Image quality of a — — ⁇ (Good) reverse-printed substance FET mobility 6.0 ⁇ 10 ⁇ 4 1.2 ⁇ 10 ⁇ 3 7.3 ⁇ 10 ⁇ 4 ON/OFF ratio 8 ⁇ 10 3 1 ⁇ 10 5 1 ⁇ 10 4
  • the ink composition for forming an insulating film of the invention can be calcinated at low temperature, and applied to the production of an electronic device having a flexible film as the substrate.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thin Film Transistor (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Formation Of Insulating Films (AREA)
US12/737,145 2008-06-13 2009-06-03 Ink composition for forming insulating film and insulating film formed from the ink composition Active 2029-06-14 US8791173B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10238866B2 (en) 2014-07-29 2019-03-26 L'oreal Iontophoresis device with multi-electrode end piece

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010245379A (ja) * 2009-04-08 2010-10-28 Hitachi Chem Co Ltd 絶縁体インク、絶縁被覆層の作製方法及び半導体装置
KR101164945B1 (ko) * 2010-09-13 2012-07-12 한국과학기술원 플렉시블 소자의 제작 방법
KR20160119093A (ko) 2014-02-04 2016-10-12 로레알 적어도 2개의 구획부를 포함하는 전기 마스크
JP6169510B2 (ja) * 2014-02-27 2017-07-26 株式会社日立産機システム インクジェットプリンタ用インク
JPWO2015163076A1 (ja) * 2014-04-25 2017-04-13 株式会社ダイセル 銀粒子塗料組成物
US10522771B2 (en) 2014-12-01 2019-12-31 Samsung Electronics Co., Ltd. Composition, electronic device, and thin film transistor
KR102407114B1 (ko) * 2015-05-29 2022-06-08 삼성전자주식회사 절연액, 절연체, 박막 트랜지스터 및 전자 소자
KR102380151B1 (ko) 2015-08-31 2022-03-28 삼성전자주식회사 박막 트랜지스터, 및 이를 포함하는 전자 장치
US9828520B2 (en) * 2016-04-15 2017-11-28 Xerox Corporation Interlayer composition and devices made therefrom
TW201811940A (zh) * 2016-05-16 2018-04-01 迪愛生股份有限公司 活性能量線硬化性反向平板印刷用油墨
JP6653362B2 (ja) * 2018-08-08 2020-02-26 紀州技研工業株式会社 インクジェット用インク
JP7234668B2 (ja) * 2019-02-06 2023-03-08 コニカミノルタ株式会社 画像形成装置および画像形成方法

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510279A (en) * 1981-08-12 1985-04-09 Mitsubishi Rayon Co., Ltd. Methacrylate resin composition for optical information recording medium
EP0166588A1 (en) 1984-06-23 1986-01-02 Shikoku Chemicals Corporation Epoxy resin composition
JPH0734022A (ja) 1993-07-23 1995-02-03 Ajinomoto Co Inc 熱硬化性ソルダーレジスト用インキ組成物
JP2001192539A (ja) 2000-01-13 2001-07-17 Jsr Corp 熱硬化性樹脂組成物、その硬化物およびその硬化物を含む回路基板
JP2002040632A (ja) 2000-07-21 2002-02-06 Showa Denko Kk レジストインキ組成物
US20030064319A1 (en) * 2001-05-21 2003-04-03 Tokyo Ohka Kogyo Co., Ltd. Negative photoresist compositions for the formation of thick films, photoresist films and methods of forming bumps using the same
JP2005128346A (ja) 2003-10-24 2005-05-19 Mitsumura Printing Co Ltd カラーフィルター作製用インキ組成物
JP2005126608A (ja) 2003-10-24 2005-05-19 Mitsumura Printing Co Ltd 精密パターニング用インキ組成物
EP1698936A2 (en) 2005-03-01 2006-09-06 Rohm and Haas Electronic Materials, L.L.C. Negative-type photosensitive resin compositions
US20070120923A1 (en) * 2005-11-30 2007-05-31 Xerox Corporation Overcoat compositions, oil-based ink compositions, and processes for ink-jet recording using overcoat and oil-based ink compositions
JP2007273712A (ja) 2006-03-31 2007-10-18 Dainippon Ink & Chem Inc 電子部品の製造方法
JP2007305950A (ja) 2006-04-12 2007-11-22 Toppan Printing Co Ltd 絶縁塗料、これから形成された有機絶縁膜、その形成方法および有機トランジスタ
EP1892574A1 (en) 2006-08-21 2008-02-27 JSR Corporation Photosensitive insulating resin composition, cured product thereof and electronic component having the same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2992856B2 (ja) * 1992-07-06 1999-12-20 株式会社サクラクレパス 転写紙用印刷インキ組成物および転写紙
JP3281473B2 (ja) * 1994-01-17 2002-05-13 日本化薬株式会社 フレキシブルプリント配線板用レジストインキ組成物及びその硬化物
JP3590481B2 (ja) * 1996-08-07 2004-11-17 サカタインクス株式会社 顔料分散物及びそれを用いた被覆剤組成物
JP2002040647A (ja) * 2000-07-31 2002-02-06 Taiyo Ink Mfg Ltd レジストインキ組成物
EP1937785A1 (en) * 2005-08-31 2008-07-02 Printar Ltd. Uv curable hybridcuring ink jet ink composition and solder mask using the same
JP5399603B2 (ja) * 2005-10-07 2014-01-29 昭和電工株式会社 シリコーンパウダーを含む熱硬化性樹脂組成物
JP5506010B2 (ja) * 2006-03-17 2014-05-28 昭和電工株式会社 樹脂組成物
JP5326236B2 (ja) * 2006-10-26 2013-10-30 日立化成株式会社 インク、液晶表示装置用スペーサの形成方法及び液晶表示装置

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4510279A (en) * 1981-08-12 1985-04-09 Mitsubishi Rayon Co., Ltd. Methacrylate resin composition for optical information recording medium
EP0166588A1 (en) 1984-06-23 1986-01-02 Shikoku Chemicals Corporation Epoxy resin composition
JPH0734022A (ja) 1993-07-23 1995-02-03 Ajinomoto Co Inc 熱硬化性ソルダーレジスト用インキ組成物
JP2001192539A (ja) 2000-01-13 2001-07-17 Jsr Corp 熱硬化性樹脂組成物、その硬化物およびその硬化物を含む回路基板
JP2002040632A (ja) 2000-07-21 2002-02-06 Showa Denko Kk レジストインキ組成物
US20030064319A1 (en) * 2001-05-21 2003-04-03 Tokyo Ohka Kogyo Co., Ltd. Negative photoresist compositions for the formation of thick films, photoresist films and methods of forming bumps using the same
JP2005128346A (ja) 2003-10-24 2005-05-19 Mitsumura Printing Co Ltd カラーフィルター作製用インキ組成物
JP2005126608A (ja) 2003-10-24 2005-05-19 Mitsumura Printing Co Ltd 精密パターニング用インキ組成物
EP1698936A2 (en) 2005-03-01 2006-09-06 Rohm and Haas Electronic Materials, L.L.C. Negative-type photosensitive resin compositions
US20060199099A1 (en) * 2005-03-01 2006-09-07 Rohm And Haas Electronic Materials Llc Negative-type photosensitive resin composition containing epoxy-containing material
US20070120923A1 (en) * 2005-11-30 2007-05-31 Xerox Corporation Overcoat compositions, oil-based ink compositions, and processes for ink-jet recording using overcoat and oil-based ink compositions
JP2007273712A (ja) 2006-03-31 2007-10-18 Dainippon Ink & Chem Inc 電子部品の製造方法
JP2007305950A (ja) 2006-04-12 2007-11-22 Toppan Printing Co Ltd 絶縁塗料、これから形成された有機絶縁膜、その形成方法および有機トランジスタ
EP1892574A1 (en) 2006-08-21 2008-02-27 JSR Corporation Photosensitive insulating resin composition, cured product thereof and electronic component having the same

Non-Patent Citations (14)

* Cited by examiner, † Cited by third party
Title
C. D. Dimitrakopoulos et al., "Organic Thin Film Transistors for Large Area Electronics," Advanced Materials, 2002, 14, No. 2, pp. 99-117.
C. Kim et al., Polymer Gate Dielectric Surface Viscoelasticity Modulates Pentacene Transistor Performance, Science, 2007, vol. 318, pp. 76-80.
D. K. Hwang et al., "Comparative studies on the stability of polymer versus Si02 gate dielectrics for pentacene thin-film transistors," Applied Physics Letters, AIP, vol. 89, No. 9, Sep. 1, 2006, pp. 093507-1 to 093507-3.
H. Klauk et al., "High-mobility polymer gate dielectric pentacene thin film transistors," Journal of Applied Physics, 2002, vol. 92, No. 9, pp. 5259-5263.
J. A. Rogers et al., "Nonphotolithographic fabrication of organic transistors with micron feature sizes," Applied Physics Letters, 1998, vol. 72, No. 21, pp. 2716-2718.
J. H. Lee et al., "Organic Thin-Film Transistors Fabricated on Plastic Substrates with a Polymeric Gate Dielectrics," Japanese Journal of Applied Physics, 2003, vol. 42, pp. L523-L525.
J. Veres et al., "Gate Insulators in Organic Field-Effect Transistors," Chemistry of Materials, 2004, 16, pp. 4543-4555.
Machine translation of JP 2005-128436. *
Notice of Reasons for Rejection mailed Mar. 16, 2010, issue for Japanese Patent Application No. 2010-501307 and Partial English translation thereof.
S. H. Kim et al., "Hysteresis-free pentacene field-effect transistors and inverters containing poly(4-vinyl phenol-co-methyl methacrylate) gate dielectrics," Applied Physics Letters, AIP, vol. 92, No. 18, May 9, 2008, pp. 183306-1 to 183306-3.
Supplementary European Search Report dated Oct. 31, 2012, issued for the corresponding European Patent Application No. 09764202.7.
T.-W. Lee et al., "Photocurable Organic Gate Insulator for the Fabrication of High-Field Effect Mobility Organic Transistors by Low Temperature and Solution Processing," Advanced Materials, vol. 19, No. 18, Sep. 17, 2007, pp. 2702-2706.
XP-002685138, Database WPI Week 200230, Thomson Scientific, London, GB; AN 2002-245992, XP002685138, -& JP 2001 192539 A (JSR CORP), Jul. 17, 2001, abstract, paragraphs [0052],[0060].
XP-002685139, Database WPI Week 200539, Thomson Scientific, London, GB, AN 2005-376945, XP002685139, -& JP 2005 128346 A (Dainippon Ink & Chem Inc) May 19, 2005, the whole document.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10238866B2 (en) 2014-07-29 2019-03-26 L'oreal Iontophoresis device with multi-electrode end piece

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EP2292707A4 (en) 2012-11-28
KR20110019367A (ko) 2011-02-25
JPWO2009150972A1 (ja) 2011-11-17
US20110086946A1 (en) 2011-04-14
EP2292707A1 (en) 2011-03-09
EP2292707B1 (en) 2017-03-08
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CN102057000B (zh) 2014-05-07
WO2009150972A1 (ja) 2009-12-17

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